Copolymers including biobased monomers and methods of making and using same

ABSTRACT

Copolymer compositions and methods for making these compositions are described. The copolymers include a vinyl aromatic monomer; a second monomer, and a biobased monomer. The second monomer is selected from the group consisting of butadiene, alkyl acrylates, alkyl methacrylates, and mixtures thereof. Examples of biobased monomers useful in the compositions include isobornyl acrylate, isobornyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, lauryl acrylate, lauryl methacrylate, and mixtures thereof. The compositions described herein can be used for binder or coating compositions and can include coating pigments, mineral fillers, and other additives.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional application of U.S. patent applicationSer. No. 13/085,933 filed Apr. 13, 2011, which claims priority to U.S.Provisional Application No. 61/333,833, filed May 12, 2010, both ofwhich are incorporated herein by reference in their entirety.

BACKGROUND

Copolymer compositions used for such purposes as binders or coatings,e.g., carpet backing and adhesives, are often made using monomersderived from oil based sources, i.e., fossil fuels. An example of such acopolymer composition using monomers derived from an oil based sourceincludes currently available styrene-butadiene copolymers. However, themovement toward environmental sustainability has provided an impetus forthe development of copolymers utilizing as much raw material fittingwithin a sustainable framework as possible. For example, the LEED GreenBuilding Rating System™ requires that materials incorporate 5% ofrapidly renewable materials. Providing binders or coatings that can beutilized in building materials to help meet the requirements of the LEEDGreen Building Rating System™ would be beneficial to the environment.However, it is also important that the binders or coatings maintain theproperties that make them beneficial for their particular use.

SUMMARY

Compositions are described herein that include a copolymer derived froma vinyl aromatic monomer, a second monomer, and a biobased monomer. Thesecond monomer is selected from the group consisting of butadiene, alkylacrylates, alkyl methacrylates, and mixtures thereof. In someembodiments, the biobased monomer can include isobornyl acrylate,isobornyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfurylmethacrylate, or mixtures thereof. In some embodiments, the biobasedmonomer can include lauryl acrylate, lauryl methacrylate, or mixturesthereof. The median particle size of the copolymer can be 200 nm orless. In some embodiments, the vinyl aromatic monomer can be present inan amount of greater than 20 weight percent based on the total(meth)acrylate content. In some embodiments, the copolymer has abiobased carbon content of 10 or greater weight percent. Thecompositions can further include a coating pigment and/or a mineralfiller and can be used in binding and coating compositions (e.g., incarpet backing).

Also described are processes for preparing a copolymer that includecopolymerizing a vinyl aromatic monomers, a second monomer, and abiobased monomer. The second monomer is selected from the groupconsisting of butadiene, alkyl acrylates, alkyl methacrylates, andmixtures thereof. In some embodiments, the biobased monomer can includeisobornyl acrylate, isobornyl methacrylate, tetrahydrofurfuryl acrylate,tetrahydrofurfuryl methacrylate, and mixtures thereof. In someembodiments, the copolymer has a biobased carbon content of 10 orgreater weight percent.

DETAILED DESCRIPTION

Copolymer compositions and methods for making these compositions aredisclosed. The compositions include one or more vinyl aromatic monomers;a second monomer, and a biobased monomer. The second monomer comprisesbutadiene, alkyl acrylates, alkyl methacrylates, or mixtures thereof.The biobased monomer comprises monomers containing biobased carbon.Examples of such biobased monomers include isobornyl acrylate, isobornylmethacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfurylmethacrylate, itaconic acid, lauryl acrylate, lauryl methacrylate, ormixtures thereof. The compositions described herein can be used forbinder or coating compositions and can include fillers, pigments, andother additives known to those of skill in the art.

Vinyl aromatic monomers useful with the compositions described hereininclude, but are not limited to, styrene, α-methylstyrene,o-chlorostyrene, vinyltoluenes, and mixtures thereof. In someembodiments, the vinyl aromatic monomer includes styrene. The copolymercan be derived from 5 or greater weight percent, 10 or greater weightpercent, 15 or greater weight percent, 20 or greater weight percent, 25or greater weight percent, 30 or greater weight percent, 35 or greaterweight percent, 40 or greater weight percent, 45 or greater weightpercent, 50 or greater weight percent, 55 or greater weight percent, 60or greater weight percent, 70 or greater weight percent, 75 or greaterweight percent, or 80 or greater weight percent of one or more vinylaromatic monomers based on the total (meth)acrylate content. In someexamples, the amount of vinyl aromatic monomer is greater than 20 weightpercent based on the total (meth)acrylate content. The total(meth)acrylate content includes the combined weight of alkyl acrylatesand alkyl methacrylates including biobased alkyl acrylates andmethacrylates. In some examples, the copolymer can be derived from 5 orgreater weight percent, 10 or greater weight percent, 15 or greaterweight percent, 20 or greater weight percent, 25 or greater weightpercent, 30 or greater weight percent, 35 or greater weight percent, 40or greater weight percent, 45 or greater weight percent, 50 or greaterweight percent, 55 or greater weight percent, 60 or greater weightpercent, 70 or greater weight percent, 75 or greater weight percent, or80 or greater weight percent of one or more vinyl aromatic monomersbased on the total monomer content.

Butadienes useful with the compositions described herein include, butare not limited to, 1,2-butadiene, 1,3-butadiene, and mixtures thereof.In some embodiments, the butadiene includes 1,3-butadiene. In someexamples, the copolymer can be derived from 0 to 45 weight percentbutadiene. For example, the copolymer can be derived from 45 weightpercent or lower, 35 weight percent or lower, 25 weight percent orlower, 20 weight percent or lower, 15 weight percent or lower, 10 weightpercent or lower, or 5 weight percent or lower of butadiene. In someexamples, the copolymer can be derived from greater than 0 weightpercent, 5 weight percent or greater, 10 weight percent or greater, 15weight percent or greater, 20 weight percent or greater, 25 weightpercent or greater, or 30 weight percent or greater of butadiene.

Alkyl acrylates and alkyl methacrylates useful with the compositionsdescribed herein include, but are not limited to, esters of C₃-C₆α,β-monoethylenically unsaturated mono- and dicarboxylic acids (e.g.,esters of acrylic acid, methacrylic acid, maleic acid, fumaric acid, oritaconic acid), and C₁-C₁₄ alkanols. Examples of useful alkyl acrylateesters and methacrylate esters include, but are not limited to, methylacrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate,n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropylmethacrylate, butyl acrylate (n-butyl acrylate, isobutyl acrylate,sec-butyl acrylate, t-butyl acrylate), butyl methacrylate (n-butylmethacrylate, isobutyl methacrylate, sec-butyl methacrylate, t-butylmethacrylate), hexyl acrylate, hexyl methacrylate, cyclohexyl acrylate,cyclohexyl methacrylate, n-octyl acrylate, n-octyl methacrylate,isooctyl acrylate, isooctyl methacrylate, 2-ethylhexyl acrylate,2-ethylhexyl methacrylate, isononyl acrylate, isononyl methacrylate,lauryl acrylate, lauryl methacrylate, and mixtures thereof. In someembodiments, the alkyl acrylate or methacrylate can include methylmethacrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, ormixtures thereof. The copolymer can be derived from 5 to 55 weightpercent of alkyl acrylates or methacrylates. For example, the copolymercan be derived from 5 weight percent or greater, 10 weight percent orgreater, 15 weight percent or greater, 20 weight percent or greater, 25weight percent or greater, 30 weight percent or greater, 35 weightpercent or greater, 40 weight percent or greater, or can be derived from55 weight percent or lower, 45 weight percent or lower, 35 weightpercent or lower, 25 weight percent or lower, 20 weight percent orlower, 15 weight percent or lower, or 10 weight percent or lower ofalkyl acrylates or methacrylates.

Biobased monomers useful with the compositions described herein includemonomers containing biobased carbon. Biobased monomers useful with thecompositions described herein include monomers containing 25 weightpercent or greater, 30 weight percent or greater, 35 weight percent orgreater, 40 weight percent or greater, 45 weight percent or greater, 50weight percent or greater, 55 weight percent or greater, 60 weightpercent or greater, 65 weight percent or greater, 70 weight percent orgreater, 75 weight percent or greater, 80 weight percent or greater, 85weight percent or greater, 90 weight percent or greater, or 95 weightpercent or greater biobased carbon (based on the total carbon content).

As used herein the term biobased carbon is intended to mean carbonobtained from a biological source rather than a fossil oil based source.The biobased content of a monomer, a copolymer, or a copolymercomposition can be determined using a method such as ASTM D6866-08. ASTMD6866-08 provides three different methods for determining the biobasedcontent of a solid, liquid, or gaseous composition. For example, thecompositions described herein can be dried as a film and tested as asolid. As defined by ASTM D6866-08, biobased content is the amount ofbiobased carbon in the material or product as a percent of the weight(mass) of the total organic carbon in the product. In particular, ASTMD6866-08 Method B measures the ratios of ¹⁴C/¹²C and ¹³C/¹²C in thecomposition using Accelerator Mass Spectrometry (AMS) and Isotope RatioMass Spectrometry (IRMS). Fossil based carbon contains essentially no¹⁴C because its age is much greater than the 5,730 year half-life of¹⁴C. Thus, the presence and level of ¹⁴C in a composition provides adirect measure of the amount of carbon that originated from a sourceother than a fossil fuel, i.e., the level of biobased carbon in thecomposition.

Examples, of biobased monomers include, but are not limited to,isobornyl acrylate, isobornyl methacrylate, tetrahydrofurfuryl acrylate,tetrahydrofurfuryl methacrylate, lauryl acrylate, lauryl methacrylate,and mixtures thereof. An example of an isobornyl acrylate includesSR506D (isobornyl acrylate) and an example of isobornyl(meth)acrylateincludes SR423D (isobornyl methacrylate) (Sartomer Company; Exton, Pa.).An example of a tetrahydrofurfuryl acrylate includes SR285(tetrahydrofurfuryl acrylate) and an example of atetrahydrofurfuryl(meth)acrylate includes SR203 (tetrahydrofurfurylmethacrylate) (Sartomer Company). The Sartomer isobornyl acrylate SR506Dcontains 76.9% biobased carbon and the Sartomer tetrahydrofurfurylacrylate SR285 contains 62.5% biobased carbon. Suitable lauryl acrylatesand methacrylates can be derived from palm oil and include, for example,AGEFLEX FM246, a lauryl methacrylate commercially available from BASFCorporation.

The copolymer can be derived from 5 or greater weight percent, 10 orgreater weight percent, 15 or greater weight percent, 20 or greaterweight percent, 25 or greater weight percent, 30 or greater weightpercent, 35 or greater weight percent, 40 or greater weight percent, 45or greater weight percent, 50 or greater weight percent, 55 or greaterweight percent, 60 or greater weight percent, 70 or greater weightpercent, 75 or greater weight percent, or 80 or greater weight percentof the biobased monomer.

The copolymers described herein can have a biobased carbon content of 10or greater weight percent. Further, the copolymer can have a biobasedcarbon content of 12 or greater weight percent, 14 or greater weightpercent, 16 or greater weight percent, 18 or greater weight percent, 20or greater weight percent, 25 or greater weight percent, 30 or greaterweight percent, 35 or greater weight percent, 40 or greater weightpercent, 45 or greater weight percent, 50 or greater weight percent, 55or greater weight percent, 60 or greater weight percent, 65 or greaterweight percent, 70 or greater weight percent, 75 or greater weightpercent, 80 or greater weight percent, 85 or greater weight percent, 90or greater weight percent, or 95 or greater weight percent of thecopolymer composition.

The amount of the biobased monomer can be selected depending upon thedesired biobased carbon amount of the copolymer. For example, if abiobased monomer used in the compositions as described herein contains40% biobased carbon and the biobased monomer is used at a 25 weightpercent level in the copolymer, the copolymer will have approximately a10% biobased carbon level. In this example, if alternative sources ofbiobased carbon are present, the copolymer could have greater than 10%biobased carbon.

The compositions described herein can include additional monomers. Insome embodiments, at least a portion of the additional monomers can alsoinclude biobased carbon to increase the overall biobased carbon contentof the copolymer.

In some embodiments, the composition includes an acid-based monomer.Acid-based monomers include, but are not limited to,α,β-monoethylenically unsaturated mono- and dicarboxylic acids, e.g.,itaconic acid, acrylic acid, methacrylic acid, crotonic acid,dimethacrylic acid, ethylacrylic acid, allylacetic acid, vinylaceticacid, maleic acid, fumaric acid, mesaconic acid, methylenemalonic acid,citraconic acid, and mixtures thereof. In some embodiments, theacid-based monomer includes itaconic acid, acrylic acid, methacrylicacid, and mixtures thereof. The itaconic acid can include biobasedcarbon. For example, the itaconic acid can be produced by an enzymaticprocess using carbohydrates (i.e., biobased materials such as cornstarch) as a carbon source. Biobased itaconic acid is available, forexample, from Sigma-Aldrich Company.

Additional monomers suitable for use in the copolymer includeacrylamides and alkyl-substituted acrylamides (e.g., (meth)acrylamide,N-tert-butylacrylamide, and N-methyl(meth)acrylamide);(meth)acrylonitrile; isoprene; anhydrides of α,β-monoethylenicallyunsaturated mono- and dicarboxylic acids (e.g., maleic anhydride,itaconic anhydride, and methylmalonic anhydride); vinyl and vinylidenehalides (e.g., vinyl chloride and vinylidene chloride); vinyl esters ofC1-C18 mono- or dicarboxylic acids (e.g., vinyl acetate, vinylpropionate, vinyl n-butyrate, vinyl laurate and vinyl stearate); C1-C4hydroxyalkyl esters of C3-C6 mono- or dicarboxylic acids, especially ofacrylic acid, methacrylic acid or maleic acid, or their derivativesalkoxylated with from 2 to 50 moles of ethylene oxide, propylene oxide,butylene oxide or mixtures thereof, or esters of these acids with C1-C18alcohols alkoxylated with from 2 to 50 mol of ethylene oxide, propyleneoxide, butylene oxide or mixtures thereof (e.g.,hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, andmethylpolyglycol acrylate); and monomers containing glycidyl groups(e.g., glycidyl methacrylate).

Further additional monomers suitable for use in the compositions caninclude linear 1-olefins, branched-chain 1-olefins or cyclic olefins(e.g., ethene, propene, butene, isobutene, pentene, cyclopentene,hexene, and cyclohexene); vinyl and allyl alkyl ethers having 1 to 40carbon atoms in the alkyl radical, wherein the alkyl radical canpossibly carry further substituents such as a hydroxyl group, an aminoor dialkylamino group, or one or more alkoxylated groups (e.g., methylvinyl ether, ethyl vinyl ether, propyl vinyl ether, isobutyl vinylether, 2-ethylhexyl vinyl ether, vinyl cyclohexyl ether, vinyl4-hydroxybutyl ether, decyl vinyl ether, dodecyl vinyl ether, octadecylvinyl ether, 2-(diethylamino)ethyl vinyl ether, 2-(di-n-butylamino)ethylvinyl ether, methyldiglycol vinyl ether, and the corresponding allylethers); sulfo-functional monomers (e.g., allylsulfonic acid,methallylsulfonic acid, styrenesulfonate, vinylsulfonic acid,allyloxybenzenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid,and their corresponding alkali metal or ammonium salts, sulfopropylacrylate and sulfopropyl methacrylate); vinylphosphonic acid, dimethylvinylphosphonate, and other phosphorus monomers;alkylaminoalkyl(meth)acrylates or alkylaminoalkyl(meth)acrylamides orquaternization products thereof (e.g.,2-(N,N-dimethylamino)ethyl(meth)acrylate,3-(N,N-dimethylamino)propyl(meth)acrylate,2-(N,N,N-trimethylammonium)ethyl(meth)acrylate chloride,2-dimethylaminoethyl(meth)acrylamide,3-dimethylaminopropyl(meth)acrylamide, and3-trimethylammoniumpropyl(meth)acrylamide chloride); allyl esters ofC1-C30 monocarboxylic acids; N-Vinyl compounds (e.g., N-vinylformamide,N-vinyl-N-methylformamide, N-vinylpyrrolidone, N-vinylimidazole,1-vinyl-2-methylimidazole, 1-vinyl-2-methylimidazoline,N-vinylcaprolactam, vinylcarbazole, 2-vinylpyridine, and4-vinylpyridine); monomers containing 1,3-diketo groups (e.g.,acetoacetoxyethyl(meth)acrylate or diacetonacrylamide; monomerscontaining urea groups (e.g., ureidoethyl(meth)acrylate,acrylamidoglycolic acid, and methacrylamidoglycolate methyl ether); andmonomers containing silyl groups (e.g., trimethoxysilylpropylmethacrylate).

Suitable monomers can also include one or more crosslinkers such asN-alkylolamides of α,β-monoethylenically unsaturated carboxylic acidshaving 3 to 10 carbon atoms and esters thereof with alcohols having 1 to4 carbon atoms (e.g., N-methylolacrylamide andN-methylolmethacrylamide); glyoxal based crosslinkers; monomerscontaining two vinyl groups; monomers containing two vinylidene groups;and monomers containing two alkenyl groups. Exemplary crosslinkingmonomers can include diesters of dihydric alcohols withα,β-monoethylenically unsaturated monocarboxylic acids, of which in turnacrylic acid and methacrylic acid can be employed. Examples of suchmonomers containing two non-conjugated ethylenically unsaturated doublebonds can include alkylene glycol diacrylates and dimethacrylates, suchas ethylene glycol diacrylate, 1,3-butylene glycol diacrylate,1,4-butylene glycol diacrylate and propylene glycol diacrylate,divinylbenzene, vinyl methacrylate, vinyl acrylate, allyl methacrylate,allyl acrylate, diallyl maleate, diallyl fumarate andmethylenebisacrylamide. In some embodiments, the crosslinking monomerscan include alkylene glycol diacrylates and dimethacrylates, and/ordivinylbenzene. The crosslinking monomers when used in the copolymer canbe present in an amount of from 0.2 to 5 phm and are considered part ofthe total amount of monomers used in the copolymer.

In addition to the crosslinking monomers, small amounts (e.g., from 0.01to 4 phm) of molecular weight regulators, such as tert-dodecylmercaptan, can be used. Such regulators can be added to thepolymerization zone in a mixture with the monomers to be polymerized andare considered part of the total amount of monomers used in thecopolymer.

The copolymer can be a styrene acrylic copolymer, a styrene butadienecopolymer, a vinyl acrylic copolymer, or an ethylene vinyl acetatecopolymer.

In some embodiments, the copolymer can be a styrene acrylic copolymerderived from monomers including styrene, one or more biobased monomers,one or more alkyl acrylates or methacrylates, and optionally(meth)acrylic acid, itaconic acid, (meth)acrylamide,(meth)acrylonitrile, and hydroxyethyl(meth)acrylate. The one or morealkyl acrylates or methacrylates can include methyl(meth)acrylate,ethyl(meth)acrylate, n-butyl(meth)acrylate, isobutyl(meth)acrylate,tert-butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, or mixturesthereof. The styrene acrylic copolymer can include from 24 to 77 phm of(meth)acrylates, from 18 to 71 phm of styrene, from 10 to 40 phm ofbiobased monomer (e.g. isobornyl acrylate), from 0.5 to 5 phm ofacid-based monomers, from 0 to 2 phm of (meth)acrylamide, and from 0 to20 phm of (meth)acrylonitrile. The styrene acrylic copolymer can alsoinclude from 0 to 3 phm of one or more crosslinking monomers asdescribed above such as alkylene glycol diacrylates and dimethacrylates.

In some embodiments, the copolymer can be a styrene butadiene copolymerderived from monomers including styrene, butadiene, (meth)acrylamide,(meth)acrylonitrile, itaconic acid and (meth)acrylic acid. The styrenebutadiene copolymer can include from 25 to 85 phm of styrene, from 15 to80 phm of butadiene, from 10 to 40 phm of biobased monomer (e.g.isobornyl acrylate), from 0 to 6 phm of itaconic and/or (meth)acrylicacid, from 0 to 2 phm of (meth)acrylamide, and from 0 to 20 phm of(meth)acrylonitrile. The styrene butadiene copolymer can also includefrom 0 to 3 phm of one or more crosslinking monomers as described abovesuch as divinylbenzene.

In some embodiments, the copolymer can be a vinyl acrylic copolymerderived from monomers including vinyl acetate, (meth)acrylic acid,(meth)acrylic acid esters, (meth)acrylamide, (meth)acrylonitrile, andmixtures thereof. For example, the vinyl acrylic copolymer can includevinyl acetate and at least one of (meth)acrylic acid, itaconic acid,methyl(meth)acrylate, ethyl(meth)acrylate, n-butyl(meth)acrylate,isobutyl(meth)acrylate, tert-butyl(meth)acrylate,2-ethylhexyl(meth)acrylate, (meth)acrylamide, (meth)acrylonitrile, andhydroxyethyl(meth)acrylate. The vinyl acrylic copolymer can include from24 to 77 phm of (meth)acrylates, from 18 to 71 phm of vinyl acetate,from 10 to 40 phm of biobased monomer (e.g. isobornyl acrylate), from 0to 2 phm of (meth)acrylamide, and from 0 to 20 phm of(meth)acrylonitrile. The vinyl acrylic copolymer can also include from 0to 3 phm of one or more crosslinking monomers as described above such asalkylene glycol diacrylates and dimethacrylates.

In some embodiments, the copolymer can be an ethylene vinyl acetatecopolymer derived from ethylene and vinyl acetate monomers. The ethylenevinyl acetate copolymer can include from 10 to 30 phm of ethylene andfrom 70 to 90 phm of vinyl acetate. The ethylene vinyl acetate copolymercan also include from 0 to 3 phm of one or more crosslinking monomers.

In some embodiments, the monomers and the amounts that the monomers areused to form the copolymer are selected to provide a glass transitiontemperature (“Tg”) of the copolymer from −10° C. to 25° C.

The copolymer can be prepared by polymerizing the monomers usingfree-radical aqueous emulsion polymerization. The emulsionpolymerization temperature is generally from 30 to 95° C. or from 75 to90° C. The polymerization medium can include water alone or a mixture ofwater and water-miscible liquids, such as methanol. Water may be usedalone. The emulsion polymerization can be carried out either as a batch,semi-batch or continuous process. Typically, a semi-batch process isused. For example, a portion of the monomers can be heated to thepolymerization temperature and partially polymerized, and the remainderof the polymerization batch can be subsequently fed to thepolymerization zone continuously, in steps or with superposition of aconcentration gradient.

The free-radical emulsion polymerization can be carried out in thepresence of a free-radical polymerization initiator. The free-radicalpolymerization initiators that can be used in the process are all thosewhich are capable of initiating a free-radical aqueous emulsionpolymerization including alkali metal peroxydisulfates and H₂O₂, or azocompounds. Combined systems can also be used comprising at least oneorganic reducing agent and at least one peroxide and/or hydroperoxide,e.g., tert-butyl hydroperoxide and the sodium metal salt ofhydroxymethanesulfinic acid or hydrogen peroxide and ascorbic acid.Combined systems can also be used additionally containing a small amountof a metal compound which is soluble in the polymerization medium andwhose metallic component can exist in more than one oxidation state,e.g., ascorbic acid/iron(II) sulfate/hydrogen peroxide, where ascorbicacid can be replaced by the sodium metal salt of hydroxymethanesulfinicacid, sodium sulfite, sodium hydrogen sulfite or sodium metal bisulfiteand hydrogen peroxide can be replaced by tert-butyl hydroperoxide oralkali metal peroxydisulfates and/or ammonium peroxydisulfates. Ingeneral, the amount of free-radical initiator systems employed can befrom 0.1 to 2 phm, based on the total amount of the monomers to bepolymerized. The initiators can be ammonium and/or alkali metalperoxydisulfates (e.g., sodium peroxydisulfates), alone or as aconstituent of combined systems. The manner in which the free-radicalinitiator system is added to the polymerization reactor during thefree-radical aqueous emulsion polymerization is not critical. It caneither all be introduced into the polymerization reactor at thebeginning, or added continuously or stepwise as it is consumed duringthe free-radical aqueous emulsion polymerization. In detail, thisdepends in a manner known to an average person skilled in the art bothfrom the chemical nature of the initiator system and on thepolymerization temperature. For example, some may be introduced at thebeginning and the remainder may be added to the polymerization zone asit is consumed. It is also possible to carry out the free-radicalaqueous emulsion polymerization under superatmospheric or reducedpressure.

The copolymer emulsion can include, as a disperse phase, particles ofthe copolymer dispersed in water. The copolymer emulsion can be preparedwith a total solids content of from 10 to 75% by weight, 15 to 65% byweight, or 20 to 60% by weight. The copolymer dispersion can then beconcentrated if desired to provide a total solids content of 40-75% byweight. The copolymer particles can have a median particle size of from80 nm to 200 nm, or from 90 nm to 180 nm. For example, the copolymerparticles can have a median particle size of 200 nm or less, 190 nm orless, 180 nm or less, 170 nm or less, 160 nm or less, 150 nm or less,140 nm or less, 130 nm or less, 120 nm or less, 110 nm or less, 100 nmor less, or 80 nm or greater, 90 nm or greater, 100 nm or greater, 110nm or greater, 120 nm or greater, 130 nm or greater, 140 nm or greater,150 nm or greater, or 160 nm or greater. The copolymer emulsion can beconverted, in a manner known per se, to redispersible copolymer powders(e.g., spray drying, roll drying or suction-filter drying). If thecopolymer dispersion is to be dried, drying aids can be used with thedispersion. The copolymer may have a long shelf life and can beredispersed in water for use in the coating or binding formulation.

The composition can be a coating or binding formulation and can includeone or more mineral fillers and/or coating pigments. Mineral fillersgenerally have a substantial proportion of particles having a particlesize greater than 2 microns whereas coating pigments have a substantialproportion of particles having a particle size less than 2 microns. Insome embodiments, the mineral fillers and/or coating pigments can beadded to impart certain properties to a coating such as smoothness,whiteness, increased density or weight, decreased porosity, increasedopacity, flatness, glossiness, and the like. The mineral fillers and/orcoating pigments can include calcium carbonate (precipitated or ground),kaolin, clay, talc, diatomaceous earth, mica, barium sulfate, magnesiumcarbonate, vermiculite, graphite, carbon black, alumina, silicas (fumedor precipitated in powders or dispersions), colloidal silica, silicagel, titanium oxides, aluminum hydroxide, aluminum trihydrate, satinewhite, and magnesium oxide. The formulation can include exclusivelymineral fillers or coating pigments but generally includes a blend ofmineral fillers and coating pigments (e.g. weight ratios of 90:10,80:20, 70:30, 60:40, 50:50, 40:60, 30:70, 20:80 or 10:90). Exemplarycoating pigments include MIRAGLOSS 91 (a kaolin clay coating pigmentcommercially available from BASF Corporation) and HYDROCARB 90 (acalcium carbonate coating pigment commercially available from OmyaPaper). An exemplary mineral filler is a calcium carbonate mineralfiller such as DF 50 from Franklin Industrial Minerals.

In some embodiments, the formulation can include non-toxic anticorrosivepigments. Examples of such anticorrosive pigments include phosphate-typeanticorrosive pigments such as zinc phosphate, calcium phosphate,aluminum phosphate, titanium phosphate, silicon phosphate, and ortho-and fused-phosphates thereof.

In some embodiments, the formulation can include one or more dyes and/orcolored pigments to produce a colored or patterned paper or to changethe shade of the coating. Exemplary dyes can include basic dyes, aciddyes, anionic direct dyes, and cationic direct dyes. Exemplary coloredpigments include organic pigments and inorganic pigments in the form ofanionic pigment dispersions and cationic pigment dispersions.

In some embodiments, one or more thickeners (rheology modifiers) can beadded to increase the viscosity of the coating or binding formulation.Suitable thickeners include acrylic copolymer dispersions sold under theSTEROCOLL and LATEKOLL trademarks from BASF Corporation, Florham Park,N.J., hydroxyethyl cellulose, guar gum, jaguar, carrageenan, xanthan,acetan, konjac mannan, xyloglucan, urethanes and mixtures thereof. Thethickeners can be added to the paper coating or binding formulation asan aqueous dispersion or emulsion, or as a solid powder. Exemplarydispersants can include sodium polyacrylates in aqueous solution such asthose sold under the DARVAN trademark by R.T. Vanderbilt Co., Norwalk,Conn.

The coating or binding formulation described herein can includeadditives such as dispersants, initiators, stabilizers, chain transferagents, buffering agents, salts, preservatives, fire retardants, wettingagents, protective colloids, biocides, corrosion inhibitors,crosslinkers, crosslinking promoters, and lubricants.

The binding or coating composition described herein can include greaterthan 50 wt % solids, 55 to 75 wt % solids, or 60 to 70 wt % solids. Theone or more mineral fillers and/or coating pigments can be present in anamount greater than 65 wt %, 70 wt %, 80 wt %, or 90 wt % of the coatingor binding formulation. For example, the one or more mineral fillersand/or coating pigments can be present in an amount of 70 to 98 wt %, 80to 95 wt %, or 85 to 90 wt % of the total volume of the formulation. Thecopolymer can be present in an amount of 2 to 12 wt %, 4 to 10 wt %, or6 to 9 wt % of the solid content. A thickener can be present in anamount of 0 to 5 wt %, greater than 0 to 3 wt %, or greater than 0 to 1wt % of the solid content. Anticorrosive pigments, dyes and coloredpigments can be present in an amount of 0 to 3 wt %, 0 to 2 wt %, or 0to 1 wt % of the solid content. Other additives can be present in anamount of 0 to 5 wt %, 0 to 3 wt %, or 0 to 1 wt % of the solid content.

The resulting compositions as described herein can be used in manyapplications and particularly as binding or coating compositions. Forexample, the compositions as described herein can be used as papercoatings, carpet backing, paints, surface coatings, and binders. Whenused as carpet backing the compositions as described herein can meet thelow VOC limit requirements of the carpet industry (e.g., less than 75ppm total of unreacted monomers such as styrene, ethylbenzene, 4-VCH(4-vinylcyclohexene), and 4-PCH (4-phenylcyclohexene); of this 75 ppmless than 50 ppm of either 4-VCH or 4-PCH, less than 40 ppm styrene, andless than 5 ppm ethylbenzene). Additionally, when used as paint, thecompositions as described herein can meet the low VOC limit requirementsof the paint industry set forth in EPA Method 24 (e.g., less than 50 g/lVOC's or even less than 10 g/l VOC's). Further, when used as carpetbacking the compositions as described herein provide good resistance towet delamination. When used as components of interior finishingproducts, e.g., carpet backing, the biobased content of the compositionsas described herein provides valuable points toward certification in theLEED Green Building Rating System™.

The compositions will now be described by the following non-limitingexamples. In the examples, the term “parts” refers to “dry parts” unlessotherwise indicated.

EXAMPLES Example Composition 1

Example Composition 1 was made according to the following procedure. Ina continuous feed process, a reactor was initially charged with water(57.2 parts), itaconic acid (0.9 parts), and DISOLVENE E-39 (Akzo NobelN.V.; Arnhem, Netherlands) (0.03 parts) (DISOLVENE® E-39 contains atetra sodium salt of ethylenediaminetetraacetic acid (“EDTA”) in a 39%aqueous solution). Additional water (13.3 parts) and sodium persulfate(0.7 parts), were then added to the reactor as an initiator feed over afour and a half hour time period. After beginning the addition of theinitiator feed to the reactor, an aqueous feed comprised of water (17.3parts), itaconic acid (1.1 parts), CALFAX® DB-45 (diphenyl oxidedisulfonate anionic surfactants) (0.6 parts), and tetrasodiumpyrophosphate (0.2 parts) were added to the reactor over a four hourtime period. Simultaneously, separate monomer feeds were added to thereactor to form the copolymer. The first monomer feed was butadiene (34parts). The second monomer feed contained styrene (54 parts), SULFOLE120 (Chevron Phillips Chemical Company; The Woodlands, Tex.) (SULFOLE120 contains tert-dodecyl mercaptan) (1.23 parts), and isobornylacrylate (10 parts; SARTOMER SR-506A). After the initiator, aqueous, andmonomer feed were charged to the reactor, i.e. after 4.5 hours, thecontents were partially neutralized to pH 5-6 and stripped by theaddition of 60 mL 10% NaOH, 70 ml 5% TBHP, 70 ml 5% SMBS and 800 mLwater, then, once stripped, an additional 60 mL 10% NaOH was added.Finally, at less than 40° C., 12 g of 1.4% ACTICIDE MV (Thor GroupLimited; Kent, England) (ACTICIDE MV is a biocide containing aconcentrated formulation of CIT/MIT) was added. The seed size for thepolymerization was 31.0 nm.

Example Composition 1 provides a copolymer derived from 34 wt %butadiene, about 54 wt % styrene, 2 wt % itaconic acid, and about 10 wt% isobornyl acrylate. This composition has a solids content of about53-54%, a viscosity of about 232 cps, a volume average particle size ofabout 139 nm, and a number average particle size of about 125 nm. Notincluding the biobased carbon addition from itaconic acid, ExampleComposition 1 provided about 7.8% biobased carbon content from isobornylacrylate.

Comparative Composition 1 and Example Compositions 2-13

Comparative Composition 1 and Example Compositions 2-13 were made usingthe same procedure described above for Example Composition 1 with themonomer levels indicated in Table 1 and the following exceptions.

For Comparative Composition 1, isobornyl acrylate was not used and themonomer composition was 34% butadiene, 2% itaconic acid, and 64%styrene. For Example Compositions 2-13, the seed charge was 0.74 parts,CALFAX DB-45 was used at 0.6 parts, and SULFONE 120 (tert-dodecylmercaptan) was used at the value shown in Table 1. Properties forExample Compositions 2-13 are also provided in Table 1.

Comparative Composition 2 and Example Compositions 14-25

100 parts by weight of Comparative Composition 1 and ExampleCompositions 2-13 were compounded with 200 parts by weight calciumcarbonate filler (GFP 101; Oglebay Norton Filler Products; Cleveland,Ohio) and 0.2 parts by weight sodium polyacrylate thickener (PG T-111from Para-Chem; Simpsonville, S.C.) to form Comparative Composition 2and Example Compositions 14-25, respectively. The 200 parts filler isused to provide a composition useful as a backing or adhesive layer forcarpet. The properties of these compositions are shown in Table 2. Thetotal solids content of each composition was between 75 and 85%.

As shown in Table 2, Example Compositions 14-25 have similar physicalproperties to Comparative Composition 2.

Comparative Composition 3 and Example Compositions 26-38

Films incorporating Comparative Composition 1 and Example Compositions2-13 were also compounded without the 200 parts calcium carbonate fillerto produce Comparative Composition 3 and Example Compositions 26-38,respectively. The tensile strength and % elongation for thesecompositions were measured. The data are shown in Table 3.

As shown in Table 3, Example Compositions 26-38 have similar physicalproperties to Comparative Composition 3.

Comparative Composition 4 and Example Compositions 39-50

100 parts by weight of Comparative Composition 1 and ExampleCompositions 2-13 were compounded with 600 parts by weight calciumcarbonate filler (GFP 101; Oglebay Norton Filler Products; Cleveland,Ohio), 0.5 parts by weight sodium polyacrylate thickener (PG T-111 fromPara-Chem; Simpsonville, S.C.), and 1.75 parts by weight surfactant(STANFAX 565 from Para-Chem; Simpsonville, S.C.) to form ComparativeComposition 4 and Example Compositions 39-50, respectively. The 600parts filler is used to provide a composition useful as pre-coat layerfor carpet. The compositions were frothed to limit penetration andproperties of these compositions are shown in Tables 4 and 5. The totalsolids content of each composition was 85%.

As shown in Tables 4 and 5, Example Compositions 39-50 have similarphysical properties to Comparative Composition 4.

Example Composition 51

Example Composition 51 was made according to the following procedure. Ina continuous feed process, a reactor was initially charged with water(53 parts), itaconic acid (0.5 parts), seed polymer (0.7 parts), andDISOLVENE E-39 (Akzo Nobel N.V.; Arnhem, Netherlands) (0.03 parts)(DISOLVENE® E-39 contains a tetra sodium salt ofethylenediaminetetraacetic acid (“EDTA”) in a 39% aqueous solution).Additional water (19 parts) and sodium persulfate (1.0 parts) were thenadded to the reactor as an initiator feed over a four and a half hourtime period. After beginning the addition of the initiator feed to thereactor, an aqueous feed comprised of water (15 parts), itaconic acid(1.5 parts), CALFAX® DB-45 (diphenyl oxide disulfonate anionicsurfactants) (0.7 parts), and tetrasodium pyrophosphate (0.2 parts) wereadded to the reactor over a four hour time period. Simultaneously,separate monomer feeds were added to the reactor to form the copolymer.The first monomer feed was butadiene (15 parts). The second monomer feedcontained styrene (53 parts), SULFOLE 120 (Chevron Phillips ChemicalCompany; The Woodlands, Tex.) (SULFOLE 120 contains tert-dodecylmercaptan) (0.2 parts), and lauryl methacrylate (30 parts; BASF AgeflexFM246). After the initiator, aqueous, and monomer feeds were charged tothe reactor, i.e. after 4.5 hours, the contents were partiallyneutralized to pH 5-6 and stripped by the addition of 60 mL 10% NaOH, 70ml 5% TBHP, 70 ml 5% SMBS and 800 mL water, then, once stripped, anadditional 60 mL 10% NaOH was added. Finally, at less than 40° C., 12 gof 1.4% ACTICIDE MV (Thor Group Limited; Kent, England) (ACTICIDE MV isa biocide containing a concentrated formulation of CIT/MIT) was added.The seed size for the polymerization was 29.0 nm.

Example Composition 51 provides a copolymer derived from 15 wt %butadiene, about 53 wt % styrene, 2 wt % itaconic acid, and about 30 wt% lauryl methacrylate. This composition has a solids content of about53%, a pH level of 7.5, a viscosity of about 420 cps, a volume averageparticle size of about 165 nm, and a number average particle size ofabout 148 nm. The Tg of the copolymer was 15° C. Not including thebiobased carbon addition from itaconic acid, Example Composition 51provided about 23% biobased carbon content from lauryl methacrylate.

Example Compositions 52 and 53

Films incorporating Example Composition 51 were compounded with 600parts of calcium carbonate filler, as described for Example Compositions39-50, to form Example Composition 52. The resulting films had athickener demand of 5.6, a viscosity after filler of 15600 cP at 80%solids, and a froth viscosity of 32,750 cP. The tensile strength of thefilms was 1037 psi with a % elongation at break of 3.2%.

Films incorporating Example Composition 51 were compounded with 200parts of calcium carbonate filler, as described for Examples 14-25, toform Example Composition 53. The resulting films had a thickener demandof 7.5, and a viscosity of 10,200 cP at 55% solids. The dry strength ofthe films was 7.6 lbs and the wet strength was 2.2 lbs (29% retention),as measured according to the wet delamination test protocol.

The compositions and methods described herein are not limited in scopeby the embodiments disclosed herein which are intended as illustrationsof a few aspects of the compositions and methods and any embodimentswhich are functionally equivalent are within the scope of the claims.Various modifications of the compositions and methods in addition tothose shown and described herein will become apparent to those skilledin the art and are intended to fall within the scope of the appendedclaims. Further, while only certain representative combinations ofmonomers used to make a composition or method steps disclosed herein arespecifically discussed in the embodiments above, other combinations ofmonomers used to make a composition or method steps will become apparentto those skilled in the art and also are intended to fall within thescope of the appended claims. Thus a combination of monomers used tomake a composition or steps may be explicitly mentioned herein; however,other combinations of monomers used to make a composition or steps areincluded, even though not explicitly stated. The term “comprising” andvariations thereof as used herein are open, non-limiting terms. The term“including” and variations thereof as used herein mean “comprising” andvariations thereof.

TABLE 1 Example Compositions 2 to 13 Monomers Properties Example SulfoneIsobornyl Solids^(b) Viscosity^(c) Composition Butadiene 120 acrylateStyrene T_(g) ^(a) (° C.) (%) pH (cPs) 2 33 1 33 33 15 52.8 7.5 227 3 331 33 33 12 54.2 7.6 212 4 35 1 33 33 15 54.1 7.5 168 5 35 1.5 33 30.7 652.8 7.5 199 6 35 1.5 33 30.7 3 53.9 7.7 292 7 35 1 33 31 8 53.7 7.6 2468 33 1.3 33 32.7 7 53.9 7.5 241 9 33 1.3 33 32.7 10 53.4 7.6 170 10 351.3 33 30.7 3 53.2 7.4 178 11 33 1.5 33 32.5 15 53.2 7.6 208 12 35 1.333 30.7 8 53.4 7.7 153 13 33 1.5 33 32.5 8 54.2 7.6 158 ^(a)As measuredusing differential scanning calorimetry (DSC) at the mid-point of theDSC curve. ^(b)Weight measured after drying in microwave oven to removewater and other volatiles. ^(c)Brookfield viscosity.

TABLE 2 Comparative Example 2 and Example Compositions 14 to 25 ExampleThickener Dry Wet % Tensile % Composition Demand^(a) Delamination^(b)Delamination^(c) Retention^(d) Strength^(e) Elongation^(f) Comp 2 3.28.2 3.1 37.8 1516 31 14 5 7.9 2.4 30.4 1671 19 15 5 7.8 2.5 32.1 1767 1916 5.5 7.9 2.5 31.7 1467 29.4 17 5.5 7.2 3.4 47.2 1061 37.4 18 3.9 6.6 345.5 879 50 19 5.5 7.1 2.5 35.2 1301 30.2 20 4.8 7.1 2.7 38 1100 35.6 215.5 7.7 3 39 1414 22.5 22 5.9 7.2 2.3 31.9 1120 45 23 5.5 6.7 2.9 43.31234 27.4 24 5.9 6.3 2.5 39.7 1140 33.8 25 5 6.5 2.8 43.1 1076 37.9^(a)Grams of wet thickener added to produce a target viscosity ofapproximately 600 cPs ^(b)Tensile strength (pounds) measured usingInstron (90° peel). ^(c)Tensile strength (pounds) after 24 hour soak inwater measured using Instron(90° peel). ^(d)Wet delamination/drydelamination ^(e)Pounds per square inch; Instron. ^(f)Measured usingInstron.

TABLE 3 Comparative Example 3 and Example Compositions 26 to 38 ExampleTensile % Composition Strength^(a) Elongation^(b) Comp 3 2215 459 262224 331 27 2294 312 28 2280 434 29 1350 565 30 1347 643 31 2183 490 321694 562 33 1658 419 34 1656 591 36 1463 437 37 1862 512 38 1648 554^(a)Pounds per square inch; measured using Instron. ^(b)Measured usingInstron.

TABLE 4 Comparative Example 4 and Example Compositions 39 to 50 ExampleThickener Pre-thickener Initial 1 Day 5 Day Beat Froth Froth CompositionDemand^(a) Viscosity^(b) Viscosity^(b) Viscosity^(b) Viscosity^(b)Back^(c) Rate^(d) Viscosity^(e) Comp 4 2.8 3100 16200 19500 18250 1720062.2 30000 39 2.8 3200 15200 17500 16000 14800 60.6 20500 40 3.1 340015000 17000 15500 13800 63.5 21500 41 3.1 3600 15200 17000 15750 1380061.2 20500 42 2.8 3500 15800 18000 16250 14700 66.4 26500 43 1.9 450015000 16000 14000 13200 66.3 23000 44 2.5 3900 15200 17000 15250 1420061.7 23000 45 2.5 3900 15800 17500 16500 14700 65.7 26000 46 2.8 310015200 17000 16500 14200 61.9 25500 47 2.2 4100 15000 17500 15250 1460063.2 23000 48 2.8 3800 15400 17500 16750 14900 61.9 22500 49 2.8 350015400 18000 16250 14700 62.4 20750 50 2.8 3400 15600 17500 16700 1480064.2 26500 ^(a)Grams of wet thickener added to produce a targetviscosity of approximately 1600 cPs. ^(b)Brookfield viscosity (cPs).^(c)Brookfield viscosity (cPs) of compound after shearing/agitation isapplied to the 5-day old composition. ^(d)Grams per three fluid ounces(300 g of compound at the time of preparation mixed at 188 +/− 2 rpm forthree minutes then poured into three ounce cup and weighed).^(e)Brookfield viscosity (cPs) of compound mixed at 188 +/− 2 rpm'suntil a 1 oz cup weighs 26.4 +/− .2 grams.

TABLE 5 Comparative Example 4 and Example Compositions 39 to 50 ExampleTensile % Composition Strength^(a) Elongation^(b) Comp 4 1164 5.8 391154 2.6 40 1130 2.5 41 1118 4.6 42 878 9.2 43 746 12.2 44 915 6.2 45914 10.1 46 994 5.6 47 671 10.6 48 875 4.3 49 772 6.2 50 784 8.2^(a)Pounds per square inch; measured using Instron. ^(b)Measured usingInstron.

What is claimed is:
 1. A binder or coating composition comprising: (A) acopolymer derived from monomers comprising: a vinyl aromatic monomer; asecond monomer selected from the group consisting of butadiene, alkylacrylates, alkyl methacrylates, and mixtures thereof; and a biobasedmonomer, wherein the copolymer has a biobased carbon content of 10 to 95weight percent, based on the weight of the copolymer, and the medianparticle size of the copolymer is 80 nm to 200 nm; and (B) a coatingpigment, mineral filler, or mixture thereof, wherein the coatingpigment, mineral filler, or mixture thereof is present in an amount of60 to 90 weight percent, based on the weight of the binder or coatingcomposition.
 2. The binder or coating composition according to claim 1,wherein the biobased monomer includes isobornyl acrylate, isobornylmethacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfurylmethacrylate, lauryl acrylate, lauryl methacrylate, or mixtures thereof.3. The binder or coating composition of claim 1, wherein the vinylaromatic monomer is present in an amount of 20 to 80 weight percentbased on the total (meth)acrylate content.
 4. A binder or coatingcomposition comprising; (A) a copolymer derived from monomerscomprising: a vinyl aromatic monomer; a second monomer selected from thegroup consisting of butadiene, alkyl acrylates, alkyl methacrylates, andmixtures thereof; and a biobased monomer, wherein the vinyl aromaticmonomer is present in an amount of 20 to 80 weight percent based on thetotal (meth)acrylate content; and (B) a coating pigment, mineral filler,or mixture thereof, wherein the coating pigment, mineral filler, ormixture thereof is present in an amount of 65 to 90 weight percent,based on the weight of the binder or coating composition.
 5. A processfor preparing a binder or coating composition, comprising: preparing acomposition comprising copolymer by copolymerizing a vinyl aromaticmonomer; a second monomer selected from the group consisting ofbutadiene, alkyl acrylates, alkyl methacrylates, and mixtures thereof;and a biobased monomer, wherein the median particle size of thecopolymer is 80 to 200 nm, and mixing the composition with a coatingpigment, mineral filler, or mixture thereof, wherein the coatingpigment, mineral filler, or mixture thereof is present in an amount of65 to 90 weight percent, based on the weight of the binder or coatingcomposition.
 6. The process of claim 5, wherein the biobased monomerincludes isobornyl acrylate, isobornyl methacrylate, tetrahydrofurfurylacrylate, tetrahydrofurfuryl methacrylate, lauryl acrylate, laurylmethacrylate, or mixtures thereof.
 7. The binder or coating compositionof claim 1, wherein the vinyl aromatic monomer comprises styrene.
 8. Thebinder or coating composition of claim 1, wherein the biobased monomerincludes 50 to 80 weight percent biobased carbon content, based on thetotal carbon content of the biobased monomer.
 9. The binder or coatingcomposition of claim 1, wherein the biobased monomer comprises 20 to 80weight percent of the copolymer.
 10. The binder or coating compositionof claim 1, wherein the second monomer comprises butadiene.
 11. Thebinder or coating composition of claim 1, wherein the second monomercomprises an alkyl acrylate, an alkyl methacrylate, or mixtures thereof.12. The binder or coating composition of claim 11, wherein the secondmonomer comprises butyl acrylate.
 13. The binder or coating compositionof claim 1, further comprising an acid-based monomer.
 14. The binder orcoating composition of claim 13, wherein the acid-based monomercomprises itaconic acid, acrylic acid, methacrylic acid, or mixturesthereof.
 15. Carpet backing comprising the binding or coatingcomposition of claim 1.